EP0584408A2 - Verfahren zur Herstellung von Gamma-Butyrolacton - Google Patents

Verfahren zur Herstellung von Gamma-Butyrolacton Download PDF

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Publication number
EP0584408A2
EP0584408A2 EP92202909A EP92202909A EP0584408A2 EP 0584408 A2 EP0584408 A2 EP 0584408A2 EP 92202909 A EP92202909 A EP 92202909A EP 92202909 A EP92202909 A EP 92202909A EP 0584408 A2 EP0584408 A2 EP 0584408A2
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EP
European Patent Office
Prior art keywords
butanediol
catalyst
butyrolactone
chromium
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92202909A
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English (en)
French (fr)
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EP0584408B1 (de
EP0584408A3 (en
Inventor
Tatsumi Ichiki
Kenji Kobayashi
Sadakatsu Suzuki
Hiroshi Ueno
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tonen Chemical Corp
Original Assignee
Tonen Sekiyu Kagaku KK
Tonen Chemical Corp
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Publication date
Application filed by Tonen Sekiyu Kagaku KK, Tonen Chemical Corp filed Critical Tonen Sekiyu Kagaku KK
Publication of EP0584408A2 publication Critical patent/EP0584408A2/de
Publication of EP0584408A3 publication Critical patent/EP0584408A3/en
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Publication of EP0584408B1 publication Critical patent/EP0584408B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00

Definitions

  • the present invention relates to a process for the preparation of ⁇ -butyrolactone by catalytically dehydrogenating 1,4-butanediol in a gaseous phase in the presence of a catalyst, which process allows recycling of unreacted 1,4-butanediol.
  • Gamma-butyrolactone is a useful compound as a solvent or an intermediate product for the preparation of pyrrolidones such as N-methyl pyrrolidone. Therefore, there is an eager need for a less costly and efficient process for the preparation of ⁇ -butyrolactone.
  • ⁇ -butyrolactone processes for the preparation of ⁇ -butyrolactone include a method where 1,4-butanediol is dehydrogenated in the presence of copper-chromium catalysts.
  • the present inventors found that when manganese and/or barium, and sodium and/or potassium are added to a copper-chromium catalyst, activity and selectivity of the catalyst are enhanced and the life of the catalyst is prolonged and that when this catalyst is reduced in specific conditions, the activity of the catalyst is further increased (copending U.S. Patent Application Serial No. 07/915,076, European Patent Application No. 92201986.4).
  • HBTHF 2-(4-hydroxybutoxy)-tetrahydrofuran
  • OBTHF 2-(4-oxobutoxy)-tetrahydrofuran
  • a purpose of the invention is to provide a process for the preparation of ⁇ -butyrolactone which process is less costly and efficient and allows recycling of the unreacted.
  • the present inventors have now found that even if a bottom in distillation of ⁇ -butyrolactone from a reaction mixture, which bottom contains unreacted 1,4-butanediol as well as impurities, is recycled as such in a feed in a process for the preparation of ⁇ -butyrolactone by catalytically dehydrogenating 1,4-butanediol in a gaseous phase in the presence of hydrogen using a copper-chromium catalyst, the activity, selectivity or life of the catalyst is not adversely affected at all and, in addition, that HBTHF and OBTHF may be decomposed even with a copper-chromium catalyst and may serve as a reactant for the product.
  • the present invention is a process for the preparation of ⁇ -butyrolactone by catalytically dehydrogenating 1,4-butanediol in a gaseous phase in the presence of a catalyst, characterized in that reaction is carried out in the presence of a catalyst containing copper and chromium and in the presence of hydrogen, and ⁇ -butyrolactone formed is separated from a reaction mixture and the residual part is recycled in a feed.
  • FIGS 1 and 2 are flow charts to demonstrate embodiments of the invention.
  • Figure 3 is a graph to show how HBTHF affects catalyst life.
  • the catalyst used in the process of the invention may be any known copper-chromium catalysts.
  • the catalyst preferably contains manganese and/or barium, and sodium and/or potassium in addition to copper and chromium as described in copending U.S. Patent Application Serial No. 07/915,076, or European Patent Application No. 92201986.4.
  • the other alkali metals e.g., lithium, rubidium and cesium
  • An atomic ratio of copper to chromium is preferably 0.4 to 1.8, more preferably 0.8 to 1.4.
  • Manganese is contained preferably in an amount of 1 to 10 parts by weight, more preferably 2 to 7 parts by weight, per 100 parts by weight of the total of copper and chromium.
  • Barium is contained preferably in an amount of 2 to 20 parts by weight, more preferably 2 to 10 parts by weight, per 100 parts by weight of the total of copper and chromium. When both manganese and barium are contained, their total is preferably 3 to 30 parts by weight per 100 parts by weight of the total of copper and chromium.
  • Sodium and potassium is contained preferably in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, as alkali metals, per 100 parts by weight of the total of copper and chromium.
  • a small amount of silicon may be contained up to 10 parts by weight per 100 parts by weight of the total of copper and chromium.
  • the above catalyst may be prepared as follows: copper nitrate, copper sulfate, copper chloride or copper acetate may be used as a copper source; dichromate (e.g., Na2Cr2O7), chromate or chromium nitrate as a chromium source; barium chloride, barium nitrate, manganese chloride, manganese nitrate and manganese acetate as a manganese or barium source; and carbonate, silicate (water glass) or hydroxide as a sodium or potassium source.
  • a chromium-containing solution is made basic by ammonium and admixed with a solution containing copper, and manganese and/or barium to form precipitates.
  • the precipitates thus obtained are filtrated, washed with water, dried, and then pyrolyzed at 300 to 400 °C.
  • the powder obtained is washed with an aqueous dilute acid solution, washed with water and dried.
  • To the catalyst precursor obtained is added a compound containing sodium and/or potassium, dried and calcined at 400 to 500 °C. Timing of the addition of sodium and/or potassium is not particularly limited, but these alkali metals are highly water-soluble and, therefore, are usually added after the aforesaid precipitates formed are washed with water and dried, or after the subsequent calcination.
  • molding aids such as graphite may be added if needed, and a predetermined shape is formed using a molding machine.
  • Each component exists in the form of oxide in the resultant catalyst.
  • Reduction of the catalyst may be carried out for instance as follows: nitrogen gas which generally contains about 3 % by volume of hydrogen is passed to the catalyst at a gas hourly space velocity (G.H.S.V.), reduced at normal temperature and pressure, of 4000 to 8000 hr ⁇ 1 under pressure of several kilograms per cm2 in gauge, heated at 140 to 160 °C until heat generation is not observed any more in the catalyst bed; then the hydrogen concentration and the temperature are gradually raised, and hydrogen of 100 % by volume is passed at a catalyst bed temperature of 200 °C for several hours.
  • G.H.S.V. gas hourly space velocity
  • the catalyst is subjected to the following reduction treatment. That is, (1) while an inert gas which contains 0.1 to 1 % by volume of hydrogen is passed as a reducing gas, the catalyst is preheated from a temperature below 40 °C to a temperature of from 100 to 140 °C (pre-reduction temperature), and then (2) the temperature and the hydrogen concentration are gradually raised. It is known from JP Application Laid-Open No. Hei-1-127042/89 that such reduction treatment enhances activity of copper-chromium catalyst in the preparation of 1,4-butanediol by hydrogenation of maleic diester. This treatment also has an effect of increasing activity of the Cu-Cr-Mn and/or Ba-Na and/or K catalyst in the preparation of ⁇ -butyrolactone by dehydrogenation of 1,4-butanediol.
  • a gas mixture comprising 1,4-butanediol and hydrogen may be contacted with the catalyst in any manner which may be properly selected among conventional ones, for instance, in a fixed bed, in a moving bed or in a fluidized bed. Alternatively, the gas mixture may be contacted with the catalyst batchwise.
  • the dehydrogenation is preferably conducted at a reaction temperature of 150 to 300 °C, a reaction pressure of 0 to 8 kg/cm2 in gauge pressure, a mole ratio of hydrogen to 1,4-butanediol of 0.5 to 10 and a weight hourly space velocity of 1,4-butanediol of 0.2 to 16 hour ⁇ 1.
  • ⁇ -butyrolactone formed is recovered from a reaction mixture, and then the remaining part which contains unreacted 1,4-butanediol is recycled in a feed. This is most conveniently done by distillating a reaction mixture to distil low-boiling ⁇ -butyrolactone away and recycling a residual bottom as such. However, it is preferred to recycle a fraction containing 1,4-butanediol as well as HBTHF and OBTHF with no higher molecular weight by-products or heavier products.
  • This may be done by distillating the distillation bottom after recover of ⁇ -butyrolactone and recycling a low-boiling fraction containing 1,4-butanediol and azeotropic HBTHF and OBTHF.
  • this is more conveniently done by drawing a middle fraction containing 1,4-butanediol from a middle part of a ⁇ -butyrolactone distillation column, and recycling it.
  • a distillation bottom is recycled in an evaporator for a feed 1,4-butanediol and then HBTHF and OBTHF evaporate as an azeotrope with 1,4-butanediol, while heavier materials accumulate in the evaporator, which may be drawn off properly.
  • FIG. 1 One embodiment is demonstrated in Figure 1. Catalyst is placed in reactor 1. 1,4-Butanediol is fed via conduit 11, evaporated and introduced into reactor 1. At start of operations, hydrogen gas is introduced via 12. In stationary operations, hydrogen generates and, therefore, excess hydrogen is removed from the system. A reaction mixture is transferred to gas-liquid separator 2 where hydrogen gas is separated, a part of which is recycled and excess hydrogen gas is removed via conduit 14 from the system. Meanwhile, a liquid part is sent to crude tower 3 where low-boiling materials are removed, and then to product tower 4. In the product tower, an object product ⁇ -butyrolactone is drawn from the top and condensed, a part of which is refluxed and the remaining part is taken out via conduit 15. A side stream containing 1,4-butanediol and azeotropic impurities is drawn away from a middle part 6 of the tower, and recycled via conduit 13. Heavier products are taken out from bottom 5 and separately disposed of.
  • a bottom containing 1,4-butanediol is drawn from bottom 5 and recycled as such.
  • unreacted 1.4-butanediol which contains impurities may be recycled as such without purification according to the invention. This is possible because the impurities do not adversely affect the activity, selectivity or life of the copper-chromium catalyst and because HBTHF and OBTHF are decomposed by the copper-chromium catalyst in the reaction system and, therefore, do not accumulate in the system when recycled.
  • This example is to demonstrate how impurities affect activity and selectivity of a catalyst when unreacted 1,4-butanediol containing impurities is recycled.
  • a model feed 1,4-butanediol used contained HBTHF, i.e., 2-(4-hydroxybutoxy)-tetrahydrofuran, which was contacted with a Cu-Cr-Mn-Ba-Na catalyst to produce ⁇ -butyrolactone.
  • Dihydrofuran (DHF) was reacted with 1,4-butanediol at a mole ratio of 1/10 using a catalyst Amberlyst 16 (Rohm and Haas Japan Company).
  • the product was extracted with benzene, and the benzene was then flash distilled.
  • the residue was subjected to distillation to obtain a distillate containing highly concentrated HBTHF.
  • the composition of the distillate was as follows: 88% by weight of HBTHF, 7.5 % by weight of 1,4-butanediol and 3.5 % by weight of 1,4-di-(2'-tetrahydrofuroxy)butane.
  • a catalyst used was prepared and reduced as follows:
  • Solution A To a solution of 150 g of Na2Cr2O7 ⁇ 2H2O in 900 ml of distilled water were added 225 ml of an aqueous 28 % ammonia, which is hereinafter referred to as Solution A.
  • Solution B In 900 ml of distilled water were dissolved 280 g of Cu(NO3)2 ⁇ 3H2O, 26 g of Mn(NO3)2 ⁇ 6H2O and 8 g of Ba(NO3)2, and heated to 80 °C. This solution is hereinafter referred to as Solution B.
  • Solution B was added to Solution A under stirring.
  • the resultant precipitates were filtrated, washed with water, dried and pulverized, which was then pyrolyzed at 350 °C.
  • the powder obtained was washed with an aqueous 10 % solution of acetic acid, washed with water and dried to obtain a catalyst precursor.
  • To 100 g of the catalyst precursor were added 15 g of sodium silicate (water glass No. 1), dried and then calcined at 450 °C for 3 hours, to which graphite was added in an amount of 0.5 % by weight. This was molded into pellets.
  • composition of the catalyst obtained in an oxide form which was determined in fluorescence X-ray analysis was as follows: 28.4 % by weight of Cu, 25.0 % by weight of Cr, 2.3 % by weight of Mn, 1.6 % by weight of Ba and 1.7 % by weight of Na.
  • the nitrogen gas was replaced with nitrogen containing 0.1 % by volume of hydrogen at room temperature and, subsequently, heating was started.
  • the temperature was elevated at a rate of 30 °C/hr up to 120 °C.
  • the temperature was elevated to 130 °C over one hour.
  • the temperature was then elevated from 130 °C to 140 °C over further one hour, from 140 °C to 150 °C over further one hour, and from 150 °C to 160 °C over further one hour, provided that the temperature was elevated after holding the predetermined temperature in each step until the concentration of hydrogen at the gas outlet became identical with that at the gas inlet.
  • the concentration of hydrogen was increased gradually from 0.1 % by volume to 0.3 % by volume, and maintained for 2 hours.
  • the concentration of hydrogen was further increased gradually from 0.3 % by volume to 0.5 % by volume, and then the reduction temperature was elevated from 160 °C to 170 °C over one hour. When the temperature reached 170 °C, the concentration of hydrogen was increased to 2.0 % by volume and then held for one hour.
  • the concentration of hydrogen was increased stepwise from 2.0 % by volume to 5.0 % by volume, 10.0 % by volume and 100 % by volume.
  • the hydrogen concentration was held constant for 1 or 2 hours.
  • the concentration of hydrogen reached 100 % by volume, the reduction temperature was elevated to 200 °C to end the reduction treatment.
  • a next step was started after confirmed that the hydrogen concentration at the gas outlet was identical with that at the gas outlet.
  • 1,4-Butanediol containing zero mole %, 0.26 mole %, 0.40 mole % or 0.81 mole % of HBTHF prepared in the above (1) was used as a feed.
  • hydrogen gas and the feed were passed in reaction conditions of 230 °C, atmospheric pressure, a weight hourly space velocity (W.H.S.V.) of 1,4-butanediol of 2.0 or 5.0 hour -1, and a molar ratio of H2 to the feed of 6.0 to conduct dehydrogenation reaction.
  • the reaction mixture were analyzed in gas chromatography to obtain the following results in mole percent.
  • a concentration of HBTHF in the reaction mixture was less than that in the feed ⁇ -butyrolactone in the all cases except the case where HBTHF content in the feed was 0 %, which indicates that HBTHF was partially decomposed into 1,4-butanediol, etc. in dehydrogenation conditions of 1,4-butanediol. This means that HBTHF would not accumulate in a system even when unreacted 1,4-butanediol containing HBTHF is recycled in a feed.
  • This example is to demonstrate any effect on the life of catalyst with impurities contained in a recycled feed.
  • the model feed was 1,4-butanediol containing HBTHF.
  • Dehydrogenation of 1,4-butanediol was conducted using the same catalyst as that prepared and reduced in (2) of Example 1, and a feed 1,4-butanediol containing HBTHF which was prepared in (1) of Example 1.
  • the reaction conditions were as follows: reaction temperature of 232 °C, pressure of 2 kg/cm2G, a W.H.S.V. of 1,4-butanediol of 5.0 hour ⁇ 1, and a molar ratio of H2 to the feed of 6.0.
  • the concentration of HBTHF in the feed was zero mole % in a period of from the start of the reaction to 100 hours; 0.62 mole % from 100 hours to 600 hours; and 1.02 mole % from 600 hours to 1000 hours. After 1000 hours, it was again zero mole %.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP92202909A 1992-08-25 1992-09-22 Verfahren zur Herstellung von Gamma-Butyrolacton Expired - Lifetime EP0584408B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP248560/92 1992-08-25
JP04248560A JP3095293B2 (ja) 1992-08-25 1992-08-25 γ‐ブチロラクトンの製造方法

Publications (3)

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EP0584408A2 true EP0584408A2 (de) 1994-03-02
EP0584408A3 EP0584408A3 (en) 1994-06-22
EP0584408B1 EP0584408B1 (de) 1999-01-07

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EP92202909A Expired - Lifetime EP0584408B1 (de) 1992-08-25 1992-09-22 Verfahren zur Herstellung von Gamma-Butyrolacton

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EP (1) EP0584408B1 (de)
JP (1) JP3095293B2 (de)
KR (1) KR940003946A (de)
AT (1) ATE175411T1 (de)
DE (1) DE69228114T2 (de)
ES (1) ES2127740T3 (de)
TW (1) TW360648B (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0827956A1 (de) * 1996-09-05 1998-03-11 Basf Aktiengesellschaft Verfahren zur Dehydrierung von 1,4-Butandiol zu Gamma-Butyrolacton
WO2001016126A3 (de) * 1999-09-01 2001-08-30 Basf Ag Verfahren zur herstellung von gamma-butyrolacton
CN1081948C (zh) * 1997-12-16 2002-04-03 中国石油化工集团公司 1,4－丁二醇气相脱氢制γ－丁内酯的催化剂
KR101049276B1 (ko) * 2008-09-01 2011-07-14 한국화학연구원 1,4-부탄디올로부터 감마-부티로락톤의 제조를 위한 촉매 및 이를 이용한 1,4-부탄디올로부터 감마-부티로락톤의 제조 방법
CN102580756A (zh) * 2012-03-15 2012-07-18 重庆大学 1,4-丁二醇常压脱氢制γ-丁内酯的催化剂及其制备方法
CN103204764A (zh) * 2012-01-17 2013-07-17 中国石油化学工业开发股份有限公司 异相催化剂以及联产1,4-丁二醇、γ-丁内酯和四氢呋喃的方法
CN111995601A (zh) * 2020-09-15 2020-11-27 安徽英特力工业工程技术有限公司 一种用于制备gbl的反应系统

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4470358B2 (ja) * 2002-05-28 2010-06-02 三菱化学株式会社 カルボニル化合物の製造方法
JP6378680B2 (ja) * 2013-08-01 2018-08-22 広栄化学工業株式会社 １−アルキルイミダゾール化合物の製法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2420250A (en) * 1944-09-08 1947-05-06 Monsanto Chemicals Method of preparing gammavalerolactone
JPS61246173A (ja) * 1985-04-23 1986-11-01 Idemitsu Petrochem Co Ltd γ−ブチロラクトンの製造方法
JP2874017B2 (ja) * 1990-02-09 1999-03-24 東燃株式会社 γ―ブチロラクトンの製造方法
JP2874016B2 (ja) * 1990-02-09 1999-03-24 東燃株式会社 γ―ブチロラクトンの製造法
US5110954A (en) * 1990-07-11 1992-05-05 E. I. Du Pont De Nemours And Company Dehydrogenation of diols
US5210229A (en) * 1991-07-17 1993-05-11 Tonen Chemical Corporation Process for the preparation of gamma-butyrolactone

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0827956A1 (de) * 1996-09-05 1998-03-11 Basf Aktiengesellschaft Verfahren zur Dehydrierung von 1,4-Butandiol zu Gamma-Butyrolacton
US5955620A (en) * 1996-09-05 1999-09-21 Basf Aktiengesellschaft Dehydrogenation of 1,4-butanediol to γ-butyrolactone
US6093677A (en) * 1996-09-05 2000-07-25 Basf Aktiengesellschaft Catalyst for dehydrogenating 1,4-butanediol to γ-butyrolactone
CN1081948C (zh) * 1997-12-16 2002-04-03 中国石油化工集团公司 1,4－丁二醇气相脱氢制γ－丁内酯的催化剂
WO2001016126A3 (de) * 1999-09-01 2001-08-30 Basf Ag Verfahren zur herstellung von gamma-butyrolacton
US6521763B1 (en) 1999-09-01 2003-02-18 Basf Aktiengesellschaft Method for producing gamma-butyrolactone
KR101049276B1 (ko) * 2008-09-01 2011-07-14 한국화학연구원 1,4-부탄디올로부터 감마-부티로락톤의 제조를 위한 촉매 및 이를 이용한 1,4-부탄디올로부터 감마-부티로락톤의 제조 방법
CN103204764A (zh) * 2012-01-17 2013-07-17 中国石油化学工业开发股份有限公司 异相催化剂以及联产1,4-丁二醇、γ-丁内酯和四氢呋喃的方法
CN103204764B (zh) * 2012-01-17 2015-09-02 中国石油化学工业开发股份有限公司 异相催化剂以及联产1,4-丁二醇、γ-丁内酯和四氢呋喃的方法
CN102580756A (zh) * 2012-03-15 2012-07-18 重庆大学 1,4-丁二醇常压脱氢制γ-丁内酯的催化剂及其制备方法
CN102580756B (zh) * 2012-03-15 2014-07-30 重庆大学 1，4-丁二醇常压脱氢制γ-丁内酯的催化剂制备方法
CN111995601A (zh) * 2020-09-15 2020-11-27 安徽英特力工业工程技术有限公司 一种用于制备gbl的反应系统

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Publication number Publication date
JP3095293B2 (ja) 2000-10-03
ATE175411T1 (de) 1999-01-15
EP0584408B1 (de) 1999-01-07
TW360648B (en) 1999-06-11
DE69228114T2 (de) 1999-06-02
DE69228114D1 (de) 1999-02-18
KR940003946A (ko) 1994-03-14
JPH0673042A (ja) 1994-03-15
ES2127740T3 (es) 1999-05-01
EP0584408A3 (en) 1994-06-22

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